Supported catalysts for the polymerization of olefins

ABSTRACT

Supported catalysts for the polymerization of olefins comprise the following components:  
     (A) a porous organic support functionalised with groups having active hydrogen atoms;  
     (B) an organo-metallic compound of aluminium containing heteroatoms selected from oxygen, nitrogen and sulphur; and  
     (C) a compound of a transition metal selected from those of groups IVb, Vb or VIb of the Periodic Table of the Elements, containing ligands of the cyclopentadienyl type.  
     These supported catalysts, obtainable in the form of spherical particles, can be used in the polymerization reaction of olefins either in liquid or in gas phase, thus producing polymers endowed with a controlled morphology and with a high bulk density.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a supported catalyst for thepolymerization of olefins, to the process for the preparation thereofand to the use of said supported catalyst in processes for thepolymerization of olefins.

[0003] 2. Description of the Prior Art

[0004] Homogeneous catalytic systems for the polymerization of olefinsbased on coordination complexes of a transition metal such as titanium,zirconium or hafnium with ligands of the cyclopentadienyl type areknown. Generally, these catalytic system comprise a soluble cocatalyst,such as the methylalumoxane (MAO).

[0005] These homogeneous catalytic systems show many advantages incomparison with traditional heterogeneous catalysts of the Ziegler-Nattatype. In particular, they allow a careful control of thestereoregularity degree and type, the molecular weight distribution andcomonomer distribution, besides making easier the use of higheralpha-olefins, diolefins and dienes as comonomers. Thus, new polymers orpolymers endowed with remarkably improved properties can be obtained.

[0006] However, being soluble in the reaction system, these catalyticsystems can not easily be utilized in polymerization processes which arenot carried out in solution. Furthermore, the polymers obtained byprocesses using the above mentioned catalysts, are generally not endowedwith satisfactory morphological characteristics.

[0007] In order to avoid these drawbacks, systems have been suggestedbased on supporting at least one component of the above mentionedcatalysts on insoluble solid supports. In most cases these solidsupports consist of inorganic oxides and, in particular, of silica oralumina.

[0008] In the prior art, cases are found wherein the opportunity ofusing supports of the polymeric type is foreseen.

[0009] In European patent applications EP-279 863 and EP-295 312supported homogeneous catalysts comprising methylalumoxane andbis(cyclopentadienyl)zirconium dichloride are described. Besides silicainorganic supports, organic supports consisting of polyethylene orpolystyrene have been used. In the preparation of the supportedcatalysts, use has been made of n-decane, which has the function ofprecipitating the methylalumoxane. These supported catalysts, after aprepolymerization treatment with ethylene in n-decane, have been used inthe polymerization reaction of ethylene in gas-phase. To attainacceptable results, high amounts of methylalumoxane for each gram ofsolid support have been used.

[0010] In European patent application EP-518 092 catalysts of the typemetallocene/alumoxane supported on polypropylene are described. Thesecatalysts have been used in the polymerization reaction of propylenecarried out in liquid monomer or in gas phase. Nothing is said about thebulk density of the polymers obtained.

[0011] Although these types of catalytic systems supported on polymericmaterials are useable in processes carried out in suspension or in gasphase with acceptable yields, however they do not allow polymers endowedwith good morphological characteristics to be obtained.

SUMMARY OF THE INVENTION

[0012] It has now been found by the Applicant that metallocene/alumoxanecatalytic systems can be advantageously made heterogeneous by supportingthem on functionalised porous organic supports. By this way it ispossible to obtain catalysts in form of spherical particles, endowedwith acceptable activities, able to produce polymers which duplicate theshape of the catalyst and therefore are endowed with controlledmorphology and high bulk density.

[0013] Therefore, an object of the present invention is a supportedcatalyst for the polymerization of olefins comprising:

[0014] (A) a porous organic support functionalised with groups havingactive hydrogen atoms;

[0015] (B) at least one organo-metallic compound of aluminium containingat least one heteroatom selected from oxygen, nitrogen and sulphur; and

[0016] (C) at least one compound of a transition metal selected fromthose of groups IVb, Vb or VIb of the Periodic Table of the Elements,containing at least one ligand of the cyclopentadienyl type.

[0017] Another object of the present invention is a process for thepreparation of a supported catalyst according to the present invention,which process comprises the step of contacting, in an inert solvent, thecomponents (A), (B) and (C) among themselves.

[0018] Still another object of the present invention is a supported andpre-polymerized catalyst for the polymerization of olefins obtainable bysubjecting a supported catalyst according to the present invention to apre-polymerization treatment with at least one olefinic monomer.

[0019] A further object of the present invention is a process for thehomo- or co-polymerization of olefins comprising the polymerizationreaction of one or more olefinic monomers in the presence of a supportedcatalyst according to the present invention.

[0020] Still a further object of the present invention is a process forthe homo- or co-polymerization of olefins comprising the polymerizationreaction of one or more olefinic monomers in the presence of a supportedand pre-polymerized catalyst according to the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The porosity (B.E.T.) of the organic support is generally higherthan 0.2 cc/g, preferably higher than 0.5 cc/g, more preferably higherthan 1 cc/g. In particular, supports suitably useable have a porositycomprised between 1 and 3 cc/g.

[0022] The surface area (B.E.T.) of the organic support is generallyhigher than 30 n/g, preferably higher than 50 m²/g, more preferablyhigher than 100 m²/g. In particular, the surface area can reach valuesof about 500 m²/g and over.

[0023] The organic support is preferably in form of particles havingcontrolled morphology, in particular microspheroidal morphology with adiameter comprised between about 5 and 1000 μm, preferably between 10and 500 μm, more preferably between 20 and 200 μm.

[0024] Supports which can be used in the catalysts according to thepresent invention are those polymers, endowed with the above mentionedcharacteristics regarding the porosity and surface area, which showfunctional groups having active hydrogen atoms.

[0025] Examples of suitable functional groups are hydroxyl groups,primary and secondary amino groups, sulphonic groups, carboxylic groups,amido groups, N-monosubstituted amido groups, sulphonamido groups,N-monosubstituted sulphonamido groups, sulphydril groups, imido groupsand hydrazido groups.

[0026] The amount of functional groups contained in the supports isgenerally higher than 0.2 milliequivalents (meq) for each gram of solidsupport, preferably higher than 0.5 meq for each gram of solid support,more preferably is. comprised between 1 and 6 meq for each gram of solidsupport.

[0027] A class of supports particulary suitable for use in the catalystsof the present invention can be obtained from partially cross-linkedporous styrenic polymers. These supports can be prepared bycopolymerization of styrenic monomers, such as styrene,ethylvinylbenzene, vinyltoluene, methylstyrene and mixtures thereof,with comonomers able to be cross-linked, such as divinylbenzene,divinyltoluene and mixtures thereof. Preferred styrenic polymers arepartially cross-linked styrene/divinylbenzene copolymers. Methods forthe preparation of these copolymers are described, for example, in U.S.Pat. No. 4,224,415, the content of which is incorporated in the presentdescription.

[0028] Porous polymers of this type can be functionalised by means ofknown methods. The most common methods to functionalise polystyreneresins are reported in “Comprehensive Pol. Sci., Pergamon Press, pages82-85 (1989)”.

[0029] A method for the preparation of alpha-hydroxyalkylated resins isdescribed by I. Fujita et al. in “Separation Science and Technology, 26,1395-1402, (1991)”.

[0030] Functionalized porous styrenic polymers useable as supportsaccording to the present invention are, moreover, those which can bedirectly obtained from the copolymerization of styrenic monomers withcomonomers functionalized with groups containing active hydrogens ortheir precursors. Examples of these polymers are the styrenic copolymersfunctionalised with hydroxy groups, which are described in the Europeanpatent application EP-496 405.

[0031] The transition metal of groups IMb, Vb or VIb of the PeriodicTable of the Elements is preferably selected from titanium, zirconium,hafnium and vanadium, more preferably is zirconium.

[0032] Transition metal compounds useable in the supported catalystsaccording to the present invention are, for example, thecyclopentadienyl compounds of formula (I):

C₅R¹ _(5−m))R² _(m)(C₅R¹ _(5−m))_(m)MO_(p−m)  (I)

[0033] wherein M is Ti, Zr, Ef or V; the two C₅R¹ _(5−m) groups, arecyclopentadienyl rings equally or differently substituted; substituentsR¹, same or different from each other, are hydrogen, alkyl, alkenyl,aryl, alkaryl or aralkyl radicals containing from 1 to 20 carbon atomswhich may also contain Si or Ge atoms or Si(CH₃)₃ groups, or furthermoretwo or four substituents R¹ of a same cyclopentadienyl ring may form oneor two rings having from 4 to 6 carbon atoms; R² is a bridging groupwhich links the two cyclopentadienyl rings and is selected among CR³ ₂,C₂R³ ₄, SiR³ ₂, Si₂R₄, GeR³ ₂, Ge₂R³ ₄, R³ ₂SiCR³ ₂, NR¹ or PR¹, whereinthe substituents R³, same or different from is Ti, Zr, Hf or V,preferably is Zr.

[0034] In the case of m=1, particulary suitable cyclopentadienylcompounds are those wherein the groups C₅R_(5−m) are selected amongcyclopentadienyl, tetramethyl-cyclopentadienyl, indenyl,2-methyl-indenyl, 4,7-dimethyl-indenyl, 2,4,7-trimethyl-indenyl,4,5,6,7-tetrahydroindenyl, 2-methyl-4,5,6,7-tetrahydroindenyl,4,7-dimethyl-4,5,6,7-tetrahydroindenyl,2,4,7-trimethyl-4,5,6,7-tetrahydroindenyl or fluorenyl groups, R² is adivalent group selected among (CH₃)₂Si, C₂H₄ and C(CH₃)₂, andsubstituents Q are selected among chlorine atoms and C₁-C₇ hydrocarbongroups, preferably methyl groups.

[0035] Non limitative examples of cyclopentadienyl compounds of formula(I), wherein m=1, are: Me₂Si(Me₄Cp)₂MCl₂ Me₂Si(Me₄Cp)₂MMe₂Me₂C(Me₄Cp)(MeCp)MCl₂ Me₂Si(Ind)₂MCl₂ Me₂Si(Ind)₂MMe₂Me₂Si(Me₄Cp)₂MCl(OEt) C₂H₄(Ind)₂MCl₂ C₂H₄(Ind)₂MMe₂ C₂H₄(Ind)₂M(NMe₂)₂C₂H₄(H₄Ind)₂MCl₂ C₂H₄(H₄Ind)₂MMe₂ C₂H₄(H₄Ind)₂M(NMe₂)OMePh(Me)Si(Ind)₂MCl₂ Ph₂Si(Ind)₂MCl₂ Me₂C(Flu)(Cp)MCl₂ C₂H₄(Me₄Cp)₂MCl₂C₂Me₄(Ind)₂MCl₂ Me₂SiCH₂(Ind)₂MCl₂ C₂H₄(2-MeInd)₂MCl₂ C₂H₄(3-MeInd)₂MCl₂C₂H₄(4,7-Me₂Ind)₂MCl₂ C₂H₄(5,6-Me₂Ind)₂MCl C₂H₄(2,4,7-Me₃Ind)₂MCl₂C₂H₄(3,4,7-Me₃Ind)₂MCl₂ C₂H₄(2-MeH₄Ind)₂MCl₂ C₂H₄(4,7-Me₂H₄Ind)₂MCl₂C₂H₄(2,4,7-Me₃H₄Ind)₂MCl₂ C₂H₄(Benz[e]Ind)₂MCl₂C₂H₄(2-Me-Benz[e]Ind)₂MCl₂ Me₂Si(2-MeInd)₂MCl₂ Me₂Si(3-MeInd)₂MCl₂Me₂Si(4,7-Me₂Ind)₂MCl₂ Me₂Si(5,6-Me₂Ind)₂MCl Me₂Si(2,4,7-Me₃Ind)₂MCl₂Me₂Si(3,4,7-Me₃Ind)₂MCl₂ Me₂Si(2-MeH₄Ind)₂MCl₂ Me₂Si(4,7-Me₂H₄Ind)₂MCl₂Me₂Si(2,4,7-Me₃H₄Ind)₂MCl₂ Me₂Si(Flu)₂MCl₂ C₂H₄(Flu)₂MCl₂Me₂Si(Benz[e]Ind)₂MCl₂ Me₂Si(2-Me-Benz[e]Ind)₂MCl₂

[0036] Another type of transition metal compounds useable in thesupported catalysts according to the present invention, are themono-cyclopentadienyl “constrained geometry” compounds described, forexample, in European patent applications EP-416 815, EP-420 436 andEP-520 732, the content of which is incorporated in the presentdescription.

[0037] Organo-metallic compounds of aluminium useable in the supportedcatalysts according to the invention are, for example, linear, branchedor cyclic alumoxane containing at least one group of the type:

[0038] wherein the substituents R⁴, same of different form each other,are defined as R¹ or are a group —O-—Al(R⁴)₂, and optionally some R⁴ canbe halogen atoms.

[0039] In particular, it is possible to use alumoxanes of formula (II):

[0040] in case of linear compounds, wherein n is 0 or an integercomprised between 1 and 40, or alumoxanes of formula (III):

[0041] in case of cyclic compounds, wherein n is an integer comprisedbetween 2 and 40. Radicals R¹ are defined as above.

[0042] Examples of alumoxanes suitable for use in the supportedcatalysts of the present invention are those in which radicals R¹ areselected among methyl, ethyl and isobutyl groups, particularlymethylalumoxane (MAO) and isobutylalumoxane (TIBAO).

[0043] A special class of organo-metallic compounds of aluminium useablein the supported catalysts according to the invention is that ofcompounds obtainable by reaction of aluminium alkyls or alkylhydrideswith water in molar ratio comprised between 1:1 and 100:1 respectively.Compounds of this type are described in European patent applicationEP-575 875, the content of which is incorporated in the presentdescription.

[0044] Moreover, organo-metallic compounds of aluminium useable in thesupported catalysts of the invention are those of formula (IV):

[0045] wherein R¹ is defined as above.

[0046] The molar ratio between the aluminium and the transition metal inthe supported catalysts of the invention is generally comprised between10 and 500, preferably between 20 and 200, more preferably between 30and 100.

[0047] The supported catalysts of the present invention can be preparedby contacting the components (A), (B) and (C) among themselves indifferent sequences.

[0048] An advantageous process for the preparation of a supportedcatalysts according to the present invention comprises contacting in aninert solvent

[0049] (A) a porous organic support functionalised with groups havingactive hydrogen atoms, and

[0050] (B) at least one organo-metallic compound of aluminium containingat least one heteroatom selected from oxygen, nitrogen and sulphur;

[0051] thereafter contacting the thus obtained product with

[0052] (C) at least one compound of a transition metal selected fromthose of groups IVb, Vb or VIb of the Periodic Table of the Elements,containing at least one ligand of the cyclopentadienyl type;

[0053] and finally recovering the supported catalyst by removing thesolvent.

[0054] Another process for the preparation of a supported catalystaccording to the present invention comprises contacting in an inertsolvent

[0055] (B) at least one organo-metallic compound of aluminium containingat least one heteroatom selected from oxygen, nitrogen and sulphur, and

[0056] (C) at least one compound of a transition metal selected fromthose of groups IVb, Vb or VIb of the Periodic Table of the Elements,containing at least one ligand of the cyclopentadienyl type;

[0057] thereafter contacting the thus obtained product with

[0058] (A) a porous organic support functionalised with groups havingactive hydrogen atoms;

[0059] and finally recovering the supported catalyst by removing thesolvent.

[0060] Yet another process for the preparation of a supported catalystaccording to the present invention comprises contacting in an inertsolvent

[0061] (A) a porous organic support functionalised with groups havingactive hydrogen atoms, and

[0062] (B) at least one organo-metallic compound of aluminium containingat least one heteroatom selected from oxygen, nitrogen and sulphur;

[0063] contacting in an inert solvent

[0064] (B) at least one organo-metallic compound of aluminium containingat least one heteroatom selected from oxygen, nitrogen and sulphur, and

[0065] (C) at least one compound of a transition metal selected fromthose of groups IVb, Vb or VIb of the Periodic Table of the Elements,containing at least one ligand of the cyclopentadienyl type;

[0066] thereafter contacting the product obtained by contacting (A) and(B) with the product obtained by contacting (B) and (C); and finallyrecovering the supported catalyst by removing the solvent.

[0067] The above indicated processes for the preparation of thesupported catalysts of the invention are conducted at a temperaturewhich is generally comprised between −80 and 100° C.

[0068] The organic support can be advantageously pre-contacted withaluminium alkyl compounds of formula (VI):

R⁵ _(q)AlX_(3−q)  (VI)

[0069] wherein R⁵ is selected among alkyl, alkenyl, aryl, alkaryl andaralkyl radicals containing from 1 to 10 carbon atoms, X is selectedamong hydrogen and halogen atoms, q is an integer comprised between 1and 3.

[0070] Non limitative examples of aluminum alkyl compounds of formula(VI) are aluminium trialkyls such as trimethylaluminium,triethylaluminium, triisopropylaluminium and triisobutylaluminium;dialkylaluminium halides such as dimethylaluminium chloride,diethylaluminium chloride, diisopropylaluminium chloride anddiisobutylaluminium chloride; dialkylaluminium hydrides such asdiethylaluminium hydride and diisobutylaluminium hydride;isoprenylaluminium. A preferred aluminium alkyl compound istriisobutylaluminium.

[0071] The supported catalysts of the present invention, before beingused, can be subjected to a pre-polymerization treatment, bypre-contacting them with small amounts of at least an olefinic monomer.

[0072] The pre-polymerization treatment is generally carried out in aninorganic solvent. The amount of polymer produced in this step isgenerally comprised between 0.5 and 10 parts by weight with respect tothe weight of the supported catalyst used.

[0073] The pre-polymerization can be advantageously carried out in thepresence of aluminium alkyl compounds of formula (VI):

R⁵ _(q)AlX_(3−q)  (VI)

[0074] wherein R⁵, X and q are defined as above, or in the presence oforgano-metallic compounds of aluminium (B) as above described, inparticular alumoxanes. Aluminium alkyl compounds of formula (VI) arepreferred.

[0075] The supported catalysts of the present invention are useable inthe homo- or co-polymerization reactions of olefins.

[0076] Before the use, the supported catalysts of the invention and, inparticular, those which are not pre-polymerized, can be advantageouslypre-contacted with alkyl aluminium compounds of formula (VI):

R⁵ _(q)AlX_(3−q)  (VI)

[0077] wherein R⁵, X and q are defined as above, or with organo-metalliccompounds of aluminium (B) as above described, in particular alumoxanes.Aluminium alkyl compounds of formula (VI) are preferred.

[0078] The supported catalysts according to the present invention can besuitably used for the homopolymerization of ethylene and, in particular,for the preparation of HDPE.

[0079] Moreover, the supported catalysts of the invention can besuitably used for the copolymerization of ethylene with olefincomonomers and, in particular for the preparation of LLDPE.

[0080] The obtained LLDPE copolymers have a content of ethylene unitsgenerally comprised between 80 and 99% by mole. Their density isgenerally comprised between 0.87 and 0.95 cc/g and they arecharacterized by an uniform distribution of the comonomeric units withinthe polymeric chain.

[0081] Olefins which can be suitably used as comonomers in the abovesaid ethylene copolymers are alpha-olefins of formula CH₂═CHR, wherein Ris a linear or branched or cyclic radical containing from 1 to 20 carbonatoms, as well as cycloolefins.

[0082] Non-limitative examples of these olefins are propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexen, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, alkylcyclohexene,cyclopentene, cyclohexene, norbornene, 4,6-dimethyl-1-heptene.

[0083] The above ethylene copolymers can also contain small amounts ofunits deriving from polyenes, in particular from dienes, conjugated ornot, linear or cyclic, such as, for example, 1,4-hexadiene, isoprene,1,3-butadiene, 1,5-hexadiene, 1,6-heptadiene.

[0084] The ethylene copolymers contain units deriving from olefins offormula CH₂═CHR, from cycloolefins and/or from polyenes in amountsgenerally comprised from 1% to 20% by mole.

[0085] Another use of interest for the supported catalysts of thepresent invention is for the preparation of elastomeric copolymers ofethylene with α-olefins of formula CH₂═CHR, wherein R is an alkylradical containing from 1 to 10 carbon atoms, optionally containinglower proportions of units deriving from a polyene.

[0086] Saturated elastomeric copolymers obtained with the supportedcatalysts of the invention generally contain from 15% to 85% by mole ofethylene units, the rest being constituted of units of one or morealpha-olefins and/or of one non-conjugated diolefin able tocyclopolymerize.

[0087] Unsaturated elastomeric copolymers contain, besides unitsderiving from the polymerization of ethylene and alpha-olefins, alsolower proportions of unsaturated units deriving from theco-polymerization of one or more polymers. The content of unsaturatedunits is generally comprised between 0.1% and 5% by weight and,preferably, is comprised between 0.2 and 2% by weight.

[0088] The elastomeric copolymers of ethylene obtainable with thesupported catalysts of the invention are characterized by valuableproperties such as low content of ashes and a uniform distribution ofthe comonomers in the polymeric chain.

[0089] Alpha-olefins which can be suitably used as comonomers in theabove said elastomeric ethylene copolymers are, for example, propylene,1-butene, 1-hexene, 4-methyl-1-pentene.

[0090] As non conjugated olefins able to cyclopolymerize, 1,5-hexadiene,1,6-heptadiene, 2-methyl-1,5-hexadiene can be used.

[0091] Polyenes which can be used as comonomers are those comprised inthe following classes:

[0092] non-conjugated diolefins capable of cyclopolymerization such as,for example, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,5-hexadiene;

[0093] dienes capable of giving unsaturated monomeric units, inparticular conjugated dienes such as, for example, butadiene andisoprene; linear non-conjugated dienes such as, for example, trans1,4-hexadiene, cis 1,4-hexadiene, 6-methyl-1,5-heptadiene,3,7-dimethyl-1,6-octadiene, 11-methyl-1,10-dodecadiene; monocyclicdiolefins such as, for example, cis-1,5-cyclooctadiene and5-methyl-1,5-cyclooctadiene; dicyclic diolefins such as for example4,5,8,9-tetrahydroindene and 6 and/or 7-methyl-4,5,8,9-tetrahydroindene;alkenyl or alkyliden norbonenes such as for example5-ethyliden-2-norbornene, 5-isopropyliden-2-norbornene,exo-5-isopropenyl-2-norbornene; polycyclic diolefins such as forexample, dicyclopentadiene, tricyclo-[6.2.1.0^(2,7)]-4,9-undecadiene andthe 4-methyl-derivative thereof.

[0094] Still another use of interest of the supported catalysts of theinvention is for the homo- or co-polymerization of propylene andalpha-olefins such as, for example, 1-butene. Depending on the catalyticsystem used, polymers showing isotactic, syndiotactic or atacticstructure can be obtained.

[0095] A further use of interest of the supported catalysts of theinvention is for the preparation of polymers of cycloolefins. Monocyclicor polycyclic olefinic monomers can be either homopolymerized orcopolymerized also with non cyclic olefinic monomers. Not limitativeexamples of cyclo-olefinic polymers which can be prepared with thesupported catalysts of the invention are described in European patentapplications EP-501 370 and EP-407 870, the content of which isincorporated in the present description.

[0096] The polymerization processes which make use of the supportedcatalysts of the present invention can be carried out in liquid phase,in the presence or not of an inert hydrocarbon solvent. The solvent canbe aliphatic such as, for example, propane, hexane, heptane, isobutene,cyclohexane, or aromatic such as, for example, toluene.

[0097] The polymerization processes which make use of the supportedcatalysts of the present invention can be advantageously carried out ingas phase.

[0098] The polymerization temperature is generally comprised between 0°C. and 250° C. In particular, in the processes for the preparation ofHDPE and LLDPE, the polymerization temperature is generally comprisedbetween 20° C. and 150° C. and, particularly, between 40° C. and 90° C.In the processes for the preparation of elastomeric copolymers thepolymerization temperature is generally comprised between 20° C. and100° C. and, particularly, between 30° C. and 80° C.

[0099] The molecular weight of the copolymers can be varied merely byvarying the polymerization temperature, the type or the concentration ofthe catalytic components or by using molecular weight regulators suchas, for example, hydrogen.

[0100] The molecular weight distribution can be varied either usingmixtures of different metallocenes, or carrying out the polymerizationin more steps which differ in the polymerization temperature and/or inthe concentrations of the molecular weight regulator.

[0101] Polymerization yields depend on the purity of the metallocenecomponent of the catalyst. Therefore, the metallocene compounds can beused in the supported catalysts of the invention either as such, or theycan be subjected to purification treatments.

[0102] The polymers obtainable with the supported catalysts of thepresent invention are endowed with good morphological characteristicsand can be obtained in form of spherical particles having diameterswhich can be comprised between 100 and 3000 μm, depending on thecatalyst and on the polymerization conditions used.

[0103] The following examples are given to illustrate and not to limitthe invention.

Characterizations

[0104] The presence of functional groups on the supports was confirmedby I.R. analysis. The quantitative determination of the functionalgroups containing active hydrogen atoms was carried out bygas-volumetric measurement during the reaction of the supports withaluminium triethyl.

[0105] The porosities and surface areas were determined by nitrogenadsorption according to the method B.E.T. using an instrumentSORPTOMATIC 1900 by Carlo Erba, as well as by mercury porosimetry bymeans of a POROSIMETER 2000 by Carlo Erba.

[0106] The intrinsic viscosities (I.V.) were measured intetrahydronaphthalene at 135° C.

[0107] The Differential Scansion Calorimetry measurements were carriedout on an instrument DSC-7, of Perkin Elmer Co. Ltd., according to thefollowing method. About 10 mg of sample were heated at 180° C. with ascanning speed equal to 10° C./min. The sample was kept at 18° C. for 5minutes and thereafter cooled with a scanning speed equal to 10° C.Thereafter, a second scanning was carried out according to the samemodalities of the first one. The values reported are those obtained inthe second scanning.

[0108] The contents of the comonomer units in the copolymers weredetermined by I.R. analysis.

[0109] The absolute densities of the polymers were determined by densitygradient columns according to the ASTM method D-1505.

[0110] The tamped bulk density (T.B.D.) and the poured bulk density(P.B.D.) were determined according to the method DIN-53194.

Preparation of the Catalytic Components ethylene-bis(indenyl)zirconiumdichloride (A) Preparation of 1,2-bisindenylethane

[0111] The preparation described in J. Ewen, J. Am. Chem. Soc., 1987,109,6544, Suppl. mat. was followed.

[0112] Into a 2 litre two-necked round-bottomed flask, 50 g of indene(437 mmol) were dissolved under inert atmosphere with 500 ml oftetrahydrofuran and were cooled to −78° C. By slow dropping (1 hour) 175ml of n-butyllithium (2.5 M in hexane, 437.5 mmol) were added. Themixture was allowed to heat up to room temperature and was kept understirring for 4 hours. It was cooled to −78° C. and 40.42 g ofdibromoethane (215 mmol) dissolved in 100 ml of tetrahydrofuran weredropped (within 20 minutes). After the end of the addition, thetemperature was raised to 50° C., the whole was kept under stirring for12 hours, then was cooled down to room temperature and 20 ml of waterwere added. The organic phase was dried and the residue was extractedwith pentane. By evaporation under vacuum 28.65 g of product wereobtained (yield=51.6%).

(B) Preparation of ethylene-bis(indenyl)zirconium dichloride

[0113] Into a 250 ml two-necked round-bottomed flask provided withcooler, 8 g (31 mmol) of 1,2-bisindenylethane and 100 ml of anhydroustetrahydrofuran were introduced, thus obtaining a yellow solution. Aftercooling to −78° C., 40 ml of butyllithium (1.6 M in hexane, 64 mmol)were added dropwise, thus obtaining a precipitate which by heatingdissolved again thus giving a reddish-yellow solution. Into a 250 mlfour-necked round-bottomed flask, provided with cooler, 8.67 g of ZrCl₄(37.2 mmol) were introduced; this was cooled to −196° C., and in this 50ml of tetrahydrofuran were condensed (strongly exothermic reaction), themixture was allowed to heat up to room temperature and thereafter it washeated under reflux for 40 minutes. At room temperature and whilestirring, the solution of the lithium salt of bisindenylethane was addedto the solution of the adduct ZrCl₄/THF and was kept stirred for 20hours in the dark. At 0° C. gaseous HCl was bubbled in, thus obtaining ayellow solution together with a precipitate of the same colour. Thesolution was concentrated by evaporating under vacuum part of thesolvent, was cooled to −20° C. and filtered off. The precipitate wasfurther purified by extraction with dichloromethane, thus obtaining 2.3g (14.7%) of product.

ethylene-bis(4,7-dimethyl-indenyl)zirconium dichloride (A) Preparationof 4,7-dimethylindene

[0114] The synthesis was carried out according to the method describedin “Organometallics, 1990, 9, 3098” (yield 54% from p-xylene).

(B) Preparation of 1,2-bis(4,7-dimethyl-3-indenyl)ethane

[0115] 38.2 g (265 mmol) of 4,7-dimethylindene were dissolved in 350 mlof tetrahydrofuran and the temperature of the solution was raised to 0°C. Thereafter, 165 ml of n-butyl-lithium (1.6 M in hexane, 264 mmol)were added dropwise over 2.5 hours. After having allowed the whole toagain reach room temperature and whilst stirring for 4 hours, apurple-red solution of 4,7-dimethylindenyllithium was obtained. Thissolution was cooled to −70° C. and treated, dropwise for 35 minutes,with 25.3 g of 1,2-dibromethane (135 mmol) in 15 ml of tetrahydrofuran.After the temperature was raised again to room temperature, a lightyellow solution was obtained to which water was added. The organic phasewas collected and dried on Na₂SO₄. The solvent was then evaporated undervacuum and 20 g of product (yield 48%) were obtained.

(C) Preparation of rac- and meso-ethylene-bis(4,7-dimethyl-1-indenylzirconium dichloride

[0116] A suspension of 10 g of 1,2-bis(4,7-dimethyl-3-indenyl)ethane(31.8 mmol) in 80 ml of tetrahydrofuran was added through a small tubeto a solution of 2.82 g of KH (70.3 mmol) in 160 ml of tetrahydrofuran,kept under stirring. After the formation of hydrogen ceased, theresulting brown solution was separated from the excess KH. This solutionand a solution of 12 g of ZrCl4 (THF)2 (31.8 mmol) in 250 ml oftetrahydrofuran were added, dropwise, over 3 hours, by means of a smalltube, into a round bottomed flask containing 50 ml of tetrahydrofurankept under rapid stirring.

[0117] A yellow solution and a precipitate were formed. After removal ofthe solvent under vacuum, the orange-yellow residue (mixture of racemoand meso isomers in the ratio 2.33:1 at the ¹H-NMR analysis) wassubjected to extraction with CH₂C₂ until all the orange product wascompletely dissolved. The yellow solid (1.7 g) resulted in being asingle stereoisomer, that is the meso (yield 11.3%). After evaporationof CH₂Cl₂ from the orange solution, 4.9 g of an orange solidcorresponding to a mixture of 93.7% racemo and 6.3% meso isomers (Yield32.5%) was obtained. This solid was then recrystallized from toluene at−20° C.

ethylene-bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride

[0118] It was prepared according to the method described in “H. H.Brintzinger et al., J. Organomet. Chem., 288, p.63 (1985)”.

Methylalumoxane (MAO)

[0119] A commercial product (Schering, MW 1400) was used in a 30% b.w.toluene solution. After having removed the volatile fractions undervacuum, the vitreous material was ground up to obtain a white powderwhich was further treated under vacuum (0.1 mmHg) for 4 hours at atemperature of 40° C. The powder thus obtained showed good flowabilityproperties.

EXAMPLE 1

[0120] Preparation of a Polystyrenic Resin

[0121] Into a 30 litre glass reactor, equipped with thermometer, refluxcondenser, blade stirrer and thermoregulation system, an aqueoussolution consisting of:

[0122] 11 l. of distilled water

[0123] 400 ml of a ROAGIT SVM (Rohm) 5% b.w. solution in water;

[0124] 55.5 g of PROLIT C10 (Caffaro);

[0125] 11 g of sodium chloride

[0126] was introduced under nitrogen atmosphere.

[0127] The whole was stirred (350 r.p.m.) at room temperature for 1hour; thereafter an organic solution consisting of:

[0128] 5.55 l. n-octane;

[0129] 1.85 l. of toluene;

[0130] 1.55 l. of styrene;

[0131] 2.55 l. of 64% of divinylbenzene in ethylvinylbenzene;

[0132] 74 g of 75% dibenzoylperoxide in water

[0133] was introduced.

[0134] The temperature of the reactor was raised to 80° C. over 1 hour,maintained for 8 hours, then cooled again to room temperature. Theproduct obtained was subjected to repeated washing with distilled water,extraction with methanol at 50° C. and, subsequently, drying at 100 ° C.and 1 mmHg of residual pressure. 2.7 Kg of product showingmicrospheroidal morphology was obtained. The product has the followingcharacteristics:

[0135] Surface area: 370 m²/g (B.E.T.), 126 m²/g (Hg);

[0136] Porosity: 1.74 ml/g (B.E.T.), 1.92 ml/g (Hg);

[0137] Average radius of pores: 94 Å (B.E.T.), 305 Å (Hg);

[0138] Particle size distribution (P.S.D.): 0.8% 300 μm; 2.2% 300-250μm; 7.0% 250-180 μm; 10.5% 180-150 μm; 73.2% 150-106 μm; 5.5% 106-75 μm;0.8% 75 μm.

[0139] Preparation of a Functionalized Polystyrenic Support

[0140] (A) Acylation

[0141] Into a 750 ml glass reactor, provided with thermometer, refluxcondenser, blade stirrer and thermoregulation system, 300 ml of carbonsulphide and 30 g of the polystyrenic resin were introduced under anitrogen atmosphere. After having thermostatted at the temperature of12° C., 66 g (0.49 mol) of previously milled AlCl₃ and thereafter 32 mlof freshly distilled CH₃COCl were added over 1 hour. The temperature wasthen raised to 25° C. and the whole was kept stirred for 6 hours. Themixture was then transferred into a 3 litre round-bottomed flask, keptstirred, containing a mixture of about 1 Kg of milled ice and 300 ml ofHCl (37%) and was stirred for 30 minutes. The resin recovered afterfiltration was subjected to repeated washing with distilled water, thenwith acetone and finally with methanol. After drying, 34 g of productshowing microspheroidal morphology was recovered. The I.R. spectrumshowed a band centered at 1685 cm⁻¹ attributable to the carbonyl groups.

[0142] (B) Reduction

[0143] Into a 500 ml glass reactor provided with thermometer, refluxcondenser, blade stirrer, 15.2 g of the acylated resin obtained at point(A), 100 ml of dioxane, 100 ml of distilled water and 15 g of NaBH wereintroduced. The mixture was kept stirred at a temperature of 25° C. for50 hours and, after addition of further 4 g of NaBH₄ was kept stirredfor further 70 hours. The resin recovered after filtration was subjectedto repeated washing with distilled water, then with acetone and finallywith methanol. After drying, 13.4 g of product showing microspheroidalmorphology were recovered. The I.R. spectrum showed a widened bandcentered at 3440 cm⁻¹ attributable to the hydroxyl groups, while theband at 1685 cm⁻¹ of the carbonyl appeared very reduced in comparisonwith that of the resin of point (A). The content of hydroxyl groups,determined by gas-volumetric titration with aluminium triethyl, is of3.3 meg per gram of resin.

EXAMPLE 2

[0144] (A) Preparation of a Supported Catalyst

[0145] Into a 350 ml glass reactor, provided with thermometer, refluxcondenser, blade stirrer and thermoregulation system, 100 ml ofanhydrous toluene and 5.24 g of the resin obtained in example 1(B) wereintroduced. The mixture, thermostatted at 0° C. and kept stirred, wasadded over 40 minutes with 30 ml of a 1 M toluene solution ofmethylalumoxane (MAO). The mixture was reacted at a temperature of 0° C.for 1 hour, then at a temperature of 30° C. for 1 hour, thereafter at atemperature of 80° C. for 4 hours. After having cooled to 25° C., 50 mlof a toluene solution containing 221.2 mg ofethylene-bis(indenyl)-zirconium dichloride was added over 55 minutes.The temperature was raised to 30° C. and the whole was kept stirred for2 hours. A reddish solution was obtained which was allowed to decant,thus obtaining a precipitate and a colourless solution which was removedby drainage. The precipitate was repeatedly washed with anhydroustoluene and then dried under vacuum. 8 g of product showingmicrospheroidal morphology was recovered, having the followingcomposition: Zr=0.38%, Cl=0.60%, Al=9.8%.

[0146] (B) Pre-polymerization

[0147] Into a 350 ml glass reactor, provided with thermometer, refluxcondenser, blade stirrer and thermoregulation system, 150 ml ofanhydrous hexane, 1.145 g of the catalyst obtained in example 2(A) and 2ml of a heptane solution containing 5 mmol of aluminium triisobutyl(TIBAL) were introduced under anhydrous nitrogen atmosphere. The mixturewas thermostatted at 35° C. and kept stirred for 15 minutes. Thereafterethylene was supplied at a pressure of 30 mmHg for 90 minutes. Afterhaving removed the solvent by evaporation under vacuum, 5.8 g of apre-polymer showing microspheroidal morphology was recovered.

EXAMPLE 3 Ethylene/1-butene copolymerization

[0148] Into a 1.35 litre steel autoclave, provided with stirrer,manometer, temperature indicator, supplying system for the catalyst,feeding lines of monomers and thermostat, purified by washing withpropane at 70° C., 640 ml of propane and the amounts of 1-butene,ethylene and hydrogen indicated in Table 1 were introduced at roomtemperature. The suspension of the catalyst was prepared as follows. Thesolid catalyst of example 2(A) and a solution of triisobutyl aluminium(TIBAL) in 10 ml of hexane was introduced into a dropping funnel. After5 minutes at the temperature of 20° C., the suspension was injected intothe autoclave under ethylene pressure. The temperature then was broughtover 5 minutes to the value requested for the polymerization and keptconstant for the polymerization time. The total pressure was keptconstant by feeding an ethylene/1-butene mixture. The reaction was theninterrupted by quick degassing of monomers and the polymer obtained wasdried in oven at 60° C. under nitrogen stream.

[0149] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 4 Ethylene/1-butene copolymerization in gas phase

[0150] Into a 1.35 litre steel autoclave, provided with stirrer,manometer, temperature indicator, supplying system for the catalyst,feeding lines of the monomers and thermostatting jacket, purified bywashing with ethylene at 70° C., 60 g of NaCl, previously dried wereintroduced at room temperature. Thereafter, the amounts of ethylene,1-butene and hydrogen reported in Table 3 were supplied. The suspensionof the catalyst was prepared as follows. Into a dropping funnel thesolid catalyst of example 2(A) and a solution of aluminium triisobutylin 10 ml of hexane (TIBAL) was introduced. After 5 minutes, at thetemperature of 20° C., the suspension was injected into the autoclave,thermostatted at 45° C., by slight ethylene overpressure. Thetemperature was then brought in about 5 minutes to the value requestedfor the polymerization and kept constant for the duration of thepolymerization. The total pressure was kept constant by feeding anethylene/1-butene mixture. The reaction was then interrupted by quickdegassing of the monomers and the polymer obtained was washed at roomtemperature with distilled water first and thereafter with acetone, thenit was dried in oven at 60° C. under nitrogen stream.

[0151] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 5 Ethylene/1-butene copolymerization in gas phase

[0152] It was worked according to the procedure described in example 4,but using 2.019 g of the pre-polymerized solid catalyst of example 2(B)without further addition of TIBAL.

[0153] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 6

[0154] (A) Preparation of a Supported Catalyst

[0155] It was worked according to the procedure described in example2(A), but 224.2 g of rac-ethylene-bis(4.7-dimethyl-indenyl)zirconiumdichloride instead of ethylene-bis-(indenyl)zirconium dichloride wereused. 7.9 g of a product showing microspheroidal morphology wasobtained, having the following composition: Al=9.6%, Cl=0.70%, Zr=0.44%.

EXAMPLE 7 Ethylene homopolymerization

[0156] Into a 4.25 litre steel autoclave, provided with agitator,manometer, temperature indicator, supplying system for the catalyst,feeding line of monomers and thermostatting jacket, purified by washingwith propane at 70° C., 2.3 litres of propane and the amounts ofethylene and hydrogen indicated in Table 1 were introduced. Thesuspension of the catalyst was prepared as follows. Into a droppingfunnel the solid catalyst of example 6 and a solution of aluminiumtriisobutyl in 10 ml of hexane (TIBAL) was introduced. After 5 minutes,at the temperature of 20° C., the suspension was injected into theautoclave, thermostatted at 45° C., by slight ethylene overpressure. Thetemperature was then brought over about 5 minutes to the value requestedfor the polymerization and maintained constant by feeding ethylene. Thenthe reaction was ceased by quick degassing of the monomers and thepolymer obtained was dried in oven at 60° C. under nitrogen stream.

[0157] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 8 Ethylene/1-butene copolymerization

[0158] It was worked according to the procedure described in example 3,but using a 4.25 litre autoclave into which 2.3 litres of propane andthe amounts of 1-butene, ethylene and hydrogen indicated in Table 1 wereintroduced. The suspension of the catalyst, prepared as described inexample 7, was injected into the autoclave, thermostatted at 45° C., byslight ethylene overpressure.

[0159] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 9

[0160] Preparation of a Functionalized Polystyrenic Support

[0161] (A) Acylation

[0162] Into a 6 litre reactor equipped with a mechanical stirrer and athermostatting system, 4300 ml of methylene chloride and 225 g of thepolystyrenic resin prepared in example 1 were introduced. This wascooled to 10° C. and 580 g of previously ground AlCl₃ were rapidlyadded. Whilst maintaining the temperature at 10° C., 230 ml of acetylchloride were added drop-wise over 1 hour. The reaction mixture was keptstirred at 25° C. for a further 24 hours. The reaction mixture wascautiously poured into a suspension consisting of 2160 ml of distilledwater, 2160 g of water and 2160 ml of 37% HCl solution. Once theaddition was completed, it was left whilst stirring for a further 15minutes, then the solid residue was filtered and repeatedly washed withdistilled water and then acetone and then methanol. The product obtainedwas dried at 60° C.; 260 g of product was obtained. The IR spectrashowed a band centred at 1680 cm⁻¹ relating to the carbonyl group.

[0163] (B) Reduction

[0164] In a 3 litre round bottomed flask equipped with a mechanicalstirrer and a thermostatting system, 1060 ml of methanol and 260 g ofthe acylated resin prepared at point (A) was introduced. Whilstmaintaining the temperature of the suspension below 35°0 C., a solutionconsisting of 138 g of NaBH₄, 170 ml of 20% NaOH and 1060 ml ofdistilled water was added over 2 hours. This was left to react for 48hours at 25° C. and then 200 ml of acetone was slowly added to destroythe excess NaBH₄. The resin was then filtered and repeatedlysequentially washed with distilled water, acetone, methanol and acetone.This was then dried under vacuo at 6° C. for 24 hours. 234 g of productwas obtained. The IR analysis showed a enlarged band centred at 3440cm⁻¹, whilst the carbonyl band at 1680 had disappeared. The content ofhydroxyl groups, determined by gas-volumetric titration with aluminiumtriethyl, is of 1.9 meq per gram of resin. The spherical shapedparticles showed an average size of 150 μm with the following surfacearea and porosity characteristics: 327 m²/g and 0.7 ml/g with averagepore diameter of 43 Å (B.E.T.), and 144 m²/g and 1.53 ml/g with pores of212 Å (Hg).

EXAMPLE 10

[0165] (A) Preparation of a Supported Catalyst

[0166] 100 ml of toluene and 5.45 g of the support prepared in example9(3) were introduced into a 350 ml jacketed reactor equipped with ablade stirrer, thermometer, reflux condenser and a thermoregulatorsystem. The suspension was thermostatted at −5° C. and 30 ml of a 1.04Msolution of MAO (156 mg Al/g support) was added over 40 minutes. Thiswas kept at −5° C. for 1 hour then heated to 30° C. and kept at thistemperature for 1 hour and finally heated to 80° C. for 4 hours. Thewhitish sussension obtained was once again cooled to −10° C. and asolution of 50 ml of toluene and 246.1 mg of EBIZrCl₂ (9.2 mg Zr/gsupport) was added over 40 minutes. The orange coloured solution wassubsequently heated to 0° C. and kept stirred for 30 minutes and then afurther 2 hours at 30° C. After decanting the solid, the liquid wasfiltered and the residue subjected to two washings with 100 ml oftoluene and one with 100 ml of anhydrous hexane and finally dried undervacuo at 25° C. 9.0 g of spherical particles was recovered, having thefollowing composition: Zr=0.55%, Cl=1.38%, Al=9.5%.

[0167] (B) Pre-polymerization

[0168] It was worked according to the procedure described in example2(B), but using 1.33 g of the supported catalyst prepared at point (A)of this example and continuing ethylene feeding for 5 hours. 6.1 g ofpre-polymer was obtained.

EXAMPLE 11 Ethylene/1-butene copolymerization

[0169] A 2.5 l steel autoclave equipped with a blade magnetic stirrer,manometer, temperature indicator, system for loading the catalyst, feedline for the monomer and a thermostatting jacket, was purged throughpropane washing at 70° C. 5 mmols of TIBAL in 5 ml of hexane, 1260 ml ofpropane and the amounts of ethylene, propylene and hydrogen reported inTable 1 were introduced at room temperature and then the reactor washeated to 45° C. The catalytic suspension was prepared in a Schlencktube with a discharge tap at the bottom. 5 mmols of TIBAL in 5 ml ofhexane was added at a temperature of 25° C. and followed by 108 mg ofsupported catalyst from example 10(A). The reagents were contacted for 5minutes and then the suspension was introduced into the autoclave byethylene overpressure. The temperature was then raised to 50° C. andmaintained constant by feeding a mixture of ethylene/1-butene in a molarratio of 18. The polymerisation was interrupted by introducing 0.6 NL ofCO into the autoclave after rapid cooling to 30° C. The reactor was thenleft to slowly degas and the polymer obtained was dried at 60° C. undervacuo.

[0170] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 12

[0171] Ethylene Homopolymerization

[0172] A 1.35 l steel autoclave equipped with a blade magnetic stirrer,manometer, temperature indicator, system for loading the catalyst, feedline for the monomer and a thermostatting jacket, was purged throughethylene washing at 70° C. At room temperature 5 mmols of TIBAL in 700ml of hexane; the amount of ethylene reported in Table 1 was introducedand then the reactor was heated to 75° C. The catalytic suspension wasprepared in a Schlenck tube with a discharge tap at the bottom. 5 mmolsof TIBAL in 5 ml of hexane was added at a temperature of 25° C. andfollowed by 390 mg of supported catalyst from example 10(A). Thereagents were contacted for 5 minutes and then the suspension wasintroduced into the autoclave by ethylene overpressure. The temperaturewas then raised to 50° C. and maintained constant by feeding ethylene.The polymerisation was interrupted by introducing 0.6 NL of CO into theautoclave after rapid cooling to 30° C. The polymeric suspension wasfiltered and the polymer obtained was dried at 60° C. under vacuo.

[0173] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 13

[0174] Propylene Homopolymerization

[0175] A 4.25 l steel autoclave equipped with a blade magnetic stirrer,manometer, temperature indicator, system for loading the catalyst, feedline for the monomer and a thermostatting jacket, was purged throughpropylene washing at 70° C. At 40° C. in a light flow of propylene, 10mmols of TIBAL in 10 ml of hexane and 204 mg of catalyst of example10(A) were introduced. 4250 ml of propylene were then added and thetemperature was raised to 50° C. The pressure was maintained constant byfeeding propylene. After two hours the reactor was left to degas and therecuperated polymer was dried at 60° C. under vacuo. 18 g ofpolypropylene granules were obtained having the followingcharacteristics: T.B.D.  0.40 g/ml intrinsic viscosity  0.40 dl/g DSCmelting peak (II scanning)   134° C. heat of fusion (ΔH)    79 J/gxylene insolubles at 25° C. 91.2% GPC Mw  34900 g/mol Mw/Mn  2.2

EXAMPLE 14 Ethylene/1-butene copolymerization

[0176] It was worked according to the procedure described in example 11,but using 570 mg of the pre-polymerized catalyst of example 10(B)instead of the supported catalyst.

[0177] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 15

[0178] Preparation of a Supported Catalyst

[0179] Into a 350 ml jacketed reactor equipped with a blade magneticstirrer, thermometer, reflux condenser and a thermoregulator system, 100ml of toluene and 5.47 g of the support prepared in example 9(B) wereintroduced. The suspension was thermostatted at −10° C. and a solution,prereacted for 30 minutes at room temperature, consisting of 40 ml oftoluene containing 1.85 g of MAO (157 mg Al/g support) and 243.4 mg ofEBIZrCl₂ (9.7 mg Zr/g support) were added over 40 minutes. The orangecoloured suspension was subsequently heated to 0° C. over 1 hour andkept stirred for 30 minutes and then 35° C. for 2 hours. After decantingthe solid, the liquid was filtered and the residue subjected to twowashings with 100 ml of toluene and one with 100 ml of anhydrous hexaneand finally dried under vacuo at 25° C. 10.8 g of spheroidal particleswas recovered, having the following composition: Zr=0.48%, Al=7.7%,solvent=13.7%.

EXAMPLE 16 Ethylene/1-butene copolymerization

[0180] It was worked according to the procedure described in example 11,but using 121 mg of the supported catalyst prepared in example 15.

[0181] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 17

[0182] Preparation of a Supported Catalyst

[0183] Into a 350 ml jacketed reactor equipped with a blade maganeticstirrer, thermometer, reflux condenser and a thermoregulator system, 100ml of toluene and 5.6 g of the support prepared in example 9(B) wereintroduced. The suspension was thermostatted at −10° C. and 20 ml of a0.83 M MAO solution were added over 30 minutes. This was kept at −10° C.for 30 minutes then heated to 30° C. and kept at this temperature for 1hour. The whitish suspension obtained was once again cooled to 0° C. anda prereacted solution consisting of 30 ml of toluene and 261.4 mg ofEBIZrCl₂ (9.2 mg Zr/g support) and 0.88 mg of MAO, was added over 40minutes. The orange coloured solution was kept stirred for 1 hour at 0°C. Slowly (over 2 hours) the suspension was heated to 30° C. andmaintained at this temperature for 1 hour. After decanting the solid,the liquid was filtered and the residue subjected to two washings with100 ml of toluene and one with 100 ml of anhydrous hexane and finallydried under vacuo at 25° C. 5.6 g of spheroidal particles was recovered,having the following composition: Zr=0.64%, Cl=1.25%; Al=9.0%.

EXAMPLE 18 Ethylene/1-butene copolymerization

[0184] It was worked according to the procedure described in example 11,but using 165 mg of the supported catalyst prepared in example 17.

[0185] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 19

[0186] Preparation of a Supported Catalyst

[0187] 100 ml of toluene and 10.15 g of the support prepared in example9(B) were introduced into a 350 ml jacketed reactor equipped with ablade stirrer, thermometer, reflux condenser and a thermoregulatorsystem. The suspension was thermostatted at −10° C. and 50 ml of a 1.16M solution of MAO (154 mg Al/g support) was added over 50 minutes. Thiswas kept at −10° C. for 1 hour then heated to 0° C. and kept at thistemperature for 1 hour, at 30° C. for 1 hour and finally heated to 80°C. for 4 hours. The whitish suspension obtained was left to decant, theliquid separated and the solid support was subjected to two washingswith 100 ml of toluene and one with 100 ml of anhydrous hexane andfinally dried under vacuo at 25° C. After drying 13.8 g of sphericalparticles was recovered, having the following composition: Al=8.95%,solvent=7.6%.

[0188] Using the same apparatus, 5.6 g of the resin treated with MAOwere dispersed in 100 ml of anhydrous toluene and cooled to 0° C. Asolution consisting of 50 ml of toluene and 228 mg of EBDMIZrCl₂ (7.8 mgZr/g support) were added over 1 hour. The purply-red coloured solutionwas left at 0° C. for 1 hour and subsequently heated to 3° C. and keptstirred for 2 hours. After decanting the solid, the liquid was filteredand the residue subjected to two washings with 100 ml of toluene and onewith 100 ml of anhydrous hexane and finally dried under vacuo at 25° C.5.4 g of spheroidal particles was recovered, having the followingcomposition: Zr=0.44%, Cl=1.09%, Al=8.1%.

EXAMPLE 20 Ethylene/1-hexene copolymerization

[0189] A 2.5 l steel autoclave equipped with a blade magnetic stirrer,manometer, temperature indicator, system for loading the catalyst, feedline for the monomer and a thermostatting jacket, was purged throughpropane washing at 70° C. 5 mmols of TIBAL in 5 ml of hexane, 1260 ml ofpropane, 277 ml of 1-hexene and the amounts of ethylene and hydrogenreported in Table 1 were introduced at room temperature and then thereactor was heated to 55° C. The catalytic suspension was prepared in aSchlenck tube with a discharge tap at the bottom. 5 mmols of TIBAL in 5ml of hexane was added at a temperature of 25° C. and followed by 150 mgof the supported catalyst prepared in example 19. The reagents werecontacted for 5 minutes and then the suspension was introduced into theautoclave by ethylene overpressure. The temperature was then raised to60° C. and maintained constant during the polymerisation. The totalpressure was kept constant by feeding ethylene. The polymerisation wasinterrupted by introducing 0.6 NL of CO into the autoclave after rapidcooling to 30° C. The reactor was then left to slowly degas and thepolymer obtained was dried at 60° C. under vacuo.

[0190] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 21

[0191] Preparation of a Supported Catalyst

[0192] 300 ml of toluene and 30.2 g of the support prepared in example9(B) were introduced into a 750 ml jacketed reactor equipped with ablade stirrer, thermometer, reflux condenser and a thermoregulatorsystem. The suspension was thermostatted at −10° C. and 200 ml of a 0.9M solution of MAO (160 mg Al/g support) was added over 70 minutes. Thiswas kept at −10° C. for jacket, purified by washing with propylene at70° C., 2 litres of propylene and the ethylene amounts indicated inTable 3 were introduced at room temperature. The suspension of thecatalyst was prepared as described in example 4, but using 220 mg of thesupported catalyst prepared in example 21, and injected into theautoclave at room temperature by a steel vial and under propylenepressure. The temperature was then brought in about 5 minutes to thevalue requested for the polymerization and kept constant for thepolymerization time. The pressure was maintained constant by feedingethylene. Thereafter, the reaction was interrupted by a quick degassingof the monomers and the polymer obtained was dried in oven at 60° C.under nitrogen stream.

[0193] The polymerization conditions and the data relating to thecharacterization of the obtained polymer are reported in Table 3.

EXAMPLE 23 Ethylene/propylene copolymerization

[0194] It was worked according to the procedure described in example 22,but using 20 mg of the supported catalyst of example 21.

[0195] The polymerization conditions and the data relating to thecharacterization of the obtained polymer are reported in Table 3.

EXAMPLE 24

[0196] Preparation of a Functionalized Polystyrenic Support

[0197] (A) Cloromethylation

[0198] In a 500 ml 3-neek flask supplied with mechanical stirrer andwater refrigerator were placed 30 g of cross-linked poly-styrene havingthe following characteristics: Average particle size  248 μm Surfacearea (B.E.T.)  891 m²/g (Hg)  112 m²/g Porosity (B.E.T.) 2.21 ml/g (Hg)1.32 ml/g

[0199] 17.25 g of trioxane, 8.6 g of ZnCl₂, 250 ml of 37% acqueous HCland 50 ml of dioxane. A rapid stream of HCl gas was poured through thereaction mixture and it was kept out at 80° C. for 4 hour and at 100° C.for 3 hours. Than, the suspension was cooled to room temperature andwashed several time with water and Na₂CO₃ water solution. Part of thesolid compound was dried under vacuum at 60° C. and the chlorine contentwas detected resulting 6.1 wt. %.

[0200] (B) Hydrolysis

[0201] The remaining part of the wet polymer, 40 g of Na₂CO₃, 360 ml ofdioxane and 240 ml of distilled water were placed in a 1 l autoclave.The autoclave was closed and the reaction was carried out at 160-162°C., reaching a pressure of 7.5-8 bar. after 5 hours, the polymer wasfiltered at room temperature and washed many times with water, than witha mixture 1-1 water-acetone, than with acetone and finally withmethanol. After drying under vacuum at 60° C., 32 g of polymer wererecovered. The following characteristics were found: Chlorine content 1.6 wt % Functional groups 1.22 meq/g Average particle size  240 μmSurface area (B.E.T.)  621 m²/g (Hg)  118 m²/g Porosity (B.E.T.) 1.34ml/g (Hg) 1.18 ml/g IR analysis broad peak centered at 2400 cm⁻¹ (OH)

EXAMPLE 25

[0202] Preparation of a Supported Catalyst

[0203] 100 ml of toluene and 5.5 g of the support prepared in example24(B) were introduced into a 350 ml jacketed reactor equipped with ablade stirrer, thermometer, reflux condenser and a thermoregulatorsystem. The suspension was thermostatted at −10° C. and 50 ml of a 0.61M solution of MAO (151 mg Al/g support) was added over 60 minutes. Thiswas kept at −10° C. for 1 hour then heated to 0° C. and kept at thistemperature for 1 hour, at 30° C. for 1 hour and finally heated to 80°C. for 3 hours. The whitish suspension obtained was left to decant, theliquid separated and the solid support was subjected to two washingswith 100 ml of toluene and then dispersed once again in 150 ml ofanhydrous toluene. After cooling to 0° C., a solution consisting of 50ml of toluene and 230 mg of EBIZrCl₂ (9.1 mg Zr/g support) were addedover 1 hour. The reddish coloured solution was left at 0° C. for 1 hourand subsequently heated to 30° C. and kept stirred for 2 hours. Afterdecanting the solid, the liquid was filtered and the residue subjectedto two washings with 100 ml of toluene and one with 100 ml of anhydroushexane and finally dried under vacuo at 25° C. 6.4 g of spheroidalparticles was recovered, having the following composition: Zr=0.54%,Cl=1.48%, Al=5.82%.

EXAMPLE 26 Ethylene/1-butene copolymerization

[0204] It was worked according to the procedure described in example 11,but using 538 mg of the supported catalyst prepared in example 25.

[0205] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 27

[0206] Preparation of a Functionalized Polystyrenic Support

[0207] (A) Tert-butylated Polystyrene

[0208] Into a 2 litre glass reactor, equipped with thermometer, refluxcondenser, blade stirrer and thermoregulation system, an aqueoussolution consisting of:

[0209] 400 ml of distilled water

[0210] 36.2 ml of a ROAGIT SVM (Rhom) 5 wt. % solution in water

[0211] 2.25 g of PROLIT C10 (Caffaro)

[0212] 0.45 g of sodium chloride

[0213] was introduced under nitrogen atmosphere. The whole was stirredat 400 rpm at room temperature for 1 hour. Thereafter an organicsolution consisting of:

[0214] 225 ml of n-octane

[0215] 75 ml of toluene

[0216] 120 ml of 55 wt % of divinylbenzene in ethylvinylbenzene

[0217] 45 ml of p-tert-butoxystyrene (Hokko Chemical Industry)

[0218] 3.13 g of 75 wt % dibenzoylperoxide in water

[0219] was introduced.

[0220] The temperature of the reactor was raised to 80° C. over 1 hour,kept for 8 hours, then cooled to 50° C. and 700 ml of distlled waterwere added. The solid product was separated by filtration and subjectedto repeated washings with distilled water, extraction with methanol at50° C. and, subsequently, drying at 100° C. and 1 mmHg of residualpressure.

[0221] 108 g of product showing microspheroidal morphology was obtained.The product has the following characteristics: Surface area (B.E.T.) 411 m²/g (Hg)   86 m²/g Porosity (B.E.T.) 0.85 ml/g (Hg) 0.66 ml/gAverage radius pore   41 Å Average particle size  170 μm IR analysispeak at 1240 cm⁻¹ (Aryl-O-t-Bu)

[0222] (B) Hydrolysis

[0223] Into a 500 ml glass reactor, provided with thermometer, refluxcondenser, blade stirrer and thermoregulation system, 200 ml ofhydrochloric acid (37% solution) and 36.5 g of the support prepared atpoint (A) of this example were introduced. The mixture was thermostattedat 90° C. and kept stirred for 8 hours. The solid was separated andadded of 200 ml of fresly HCl and kept at 90° C. for a further 4 hours.After filtration, the recovered solid was washed with water till a pH=7of the washing, then washed with acetone and dried under vacum at 60° C.34.7 g of spherical particle were recovered, having 1.5 meq/g offunctional groups. The IR analysis shows a sharp peak at 3450 cm−1 andthe peak at 1240 cm−1 disappers.

EXAMPLE 28

[0224] Preparation of a Supported Catalyst

[0225] 100 ml of toluene and 5.3 g of the polystyrenic support preparedin example 27(B) were introduced into a 350 ml jacketed reactor equippedwith a blade stirrer, thermometer, reflux condenser and athermoregulator system. The suspension was thermostatted at 0° C. and 33ml of a toluene solution containing 5 g of triethyl aluminium. Once theaddition was completed, the solution was heated to 25° C. and keptstirred for 1 hour. After filtering the liquid phase, the solid waswashed in toluene and once again dispersed in 100 ml toluene. Thesuspension was then thermostatted at −5° C. and 25 ml of a 1.37 Msolution of MAO (176 mg Al/g support) was added over 20 minutes. Thiswas heated to 0° C. and kept at this temperature for 1 hour, at 30° C.for 1 hour and finally heated to 80° C. for 4 hours. After cooling to−10° C., 50 ml of toluene and 218 mg of EBIZrCl₂ (9.0 mg Zr/g support)was added over 1 hour. The reddish coloured solution was left at 0° C.for 1 hour and subsequently heated to 30° C. and kept stirred for 2hours. After decanting the solid, the liquid was filtered and theresidue subjected to two washings with 100 ml of toluene and one with100 ml of anhydrous hexane and finally dried under vacuo at 25° C. 6.0 gof spheroidal particles was recovered, having the following composition:Zr=0.42%, Cl=1.1%, Al=11.9%.

EXAMPLE 29 Ethylene/1-butene copolymerization

[0226] It was worked according to the procedure described in example 11but using 185 mg of the supported catalyst prepared in example 28.

[0227] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 30

[0228] Preparation of a Functionalized Polystyrenic Support

[0229] 100 ml of cyclohexane, 13.8 g of the polystyrenic resin preparedin example 1, and 17.8 ml of N,N,N′,N′-tetramethyl ethylene diamine(TMEDA) were introduced into a 350 ml jacketed reactor maintained in aninert atmosphere (N₂), equipped with a blade stirrer, thermometer,reflux condenser and a thermoregulator system. Maintaining thetemperature of the suspension at 20-22° C., 100 ml of a solution of 1.6M n-butyl lithium was fed over 1.5 hours. The suspension changed fromyellow through orange and finally red. This was then heated to 65° C.and kept at this temperature for 4.5 hours. the solid was then filtered,whilst keeping under an inert atmosphere, and subjected to two washingswith 100 ml of cyclo-hexane and then 150 ml of tetrahydrofuran (THF) wasadded previously saturated with CO₂. Then about 300 g of solid CO₂ wasdirectly added to the suspension whilst stirring continuously. Thecolour of the solution became whitish. The suspension was left to reactovernight, then filtered and the solid was subjected to repeatedwashings with a solution THF/HCl, methanol/HCl, methanol and thenfinally dried under vacuo at 40° C. 14 g of spherical resin was obtainedhaving the following characteristics: Functional groups  1.2 meq/gAverage radius pore   37 Å Average particle size  150 μm Surface area(B.E.T.)  303 m²/g (Hg)  129 m²/g Porosity (B.E.T.) 1.12 ml/g (Hg) 1.69ml/g IR analysis peak at 1700 cm⁻¹ . (—C═O) peak at 3400 cm⁻¹ (—OH)

EXAMPLE 31

[0230] Preparation of a Supported Catalyst

[0231] 100 ml of toluene and 5.7 g of the support from example 30 wereintroduced into a 350 ml jacketed reactor equipped with a blade stirrer,thermometer, reflux condenser and a thermoregulator system. Thesuspension was thermostatted at 0° C. and 10 ml of a toluene solutioncontaining 1.5 g of triethyl aluminium. Once the addition was completed,the solution was heated to 80° C. and kept stirred for 1 hour. Afterfiltering the liquid phase, the solid was washed in toluene and onceagain dispersed in 100 ml toluene. The suspension was then thermostattedat 0° C. and 50 ml of a 0.64 M solution of MAO (153 mg Al/g support) wasadded over 40 minutes. This was kept at 0° C. for 1 hour, heated to 30°C. for 1 hour and finally 80° C. for 4 hours. After cooling to roomtemperature, the suspension was filtered and once again 100 ml ofanhydrous toluene was added. The suspension was cooled to 0° C. and asolution consisting of 40 ml of toluene and 212 mg of EBIZrCl₂ (8,1 mgzr/g support) was added. The reddish coloured solution was heated to 30°C. and kept stirred for 2 hours. After decanting the solid, the liquidwas filtered and the residue subjected to two washings with 100 ml oftoluene and one with 100 ml of anhydrous hexane and finally dried undervacuo at 25° C. 5.9 g of spheroidal particles was recovered, having thefollowing composition: Zr=0.2%, Cl=0.46%, Al=7.2%.

EXAMPLE 32 Ethylene/1-butene copolymerization

[0232] It was worked according to the procedure described in example 3but using 370 mg of the supported catalyst prepared in example 31.

[0233] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 33

[0234] Preparation of a Functionalized Polystyrenic Support

[0235] (A) Methylated Polystyrene

[0236] Into a 2 litre glass reactor, equipped with thermometer, refluxcondenser, blade stirrer and thermoregulation system, an aqueoussolution consisting of:

[0237] 400 ml of distilled water

[0238] 30 ml of a ROAGIT SVM (Rhom) 5 wt. % solution in water

[0239] 2.25 g of PROLIT C10 (Caffaro)

[0240] 0.45 g of sodium chloride

[0241] was introduced under nitrogen atmosphere. The whole was stirredat 400 rpm at room temperature for 1 hour. Thereafter an organicsolution consisting of:

[0242] 225 ml of n-octane

[0243] 75 ml of toluene

[0244] 120 ml of 55 wt % of divinylbenzene in ethylvinylbenzene

[0245] 31.5 ml of m and p-methylstyrene

[0246] 3.13 g of 75 wt % dibenzoylperoxide in water

[0247] was introduced.

[0248] The temperature of the reactor was raised to 80° C. over 1 hour,kept at this temperature for 9 hours, then cooled to 50° C. and 700 mlof distilled water was added. The solid product was separated byfiltration and subjected to repeated washings with distilled water, HCl(5 wt %) solution, distilled water and extraction with methanol at 5° C.Subsequently, the solid was dried at 100° C. and 1 nmHg of residualpressure.

[0249] 117 g of product showing microspheroidal morphology was obtained.The product has the following characteristics: Average radius pore   69Å Average particle size  150 μm Surface area (B.E.T.)  495 m²/g (Hg) 137 m²/g Porosity (B.E.T.) 1.72 ml/g (Hg) 1.87 ml/g

[0250] (B) Acetylation

[0251] Into a 1500 ml glass reactor, provided with thermometer, refluxcondenser, blade stirrer and thermoregulation system, 1000 ml of aceticacid and 20 g of the support prepared at point (A) of this example wereintroduced. Slowly 56 g of Mn(OAc)₃. 3H₂O were added. Maintaining thetemperature below 4° C., 100 ml of sulphuric acid (96%) were droppedinto the stirred suspension. The mixture was then thermostatted at 45°C. and kept stirred for 4 hours. After filtration, the recovered solidwas washed with a NaHCO₃ solution, water, methyl alcohol, finally withacetone and dried under vacuo at 80° C. for 5 hours. 23 g of sphericalparticle were recovered. The IR analysis show a peak at 1740 cm⁻¹ (—C═O)and a peak at 1220 cm⁻¹ (—OAc).

[0252] (C) Hydrolysis

[0253] Into a 1 l glass reactor, provided with thermometer, refluxcondenser, blade stirrer and thermoregulation system, 500 ml of toluene,200 ml of 40 wt % KOH solution, the product prepared at point (B) ofthis example and 10 ml of 40 wt % Bu₄NOH solution in water, wereintroduced. The mixture was thermostatted at 85° C. and kept stirred for21 hours. The solid was separated and washed with 300 ml of a HCl/watersolution, then washed with distilled water, methyl alcohol, acetone anddried under vacuo at 80° C. 19 g of spherical particle were recovered.

[0254] The IR analysis showed a broad peak at 3400 cm⁻¹ and the peaks at1740 and 1220 cm⁻¹ had totally disappeared. The titration with aluminiumtriethyl indicated 1.5 meq/g of —OH group.

EXAMPLE 34

[0255] Preparation of a Supported Catalyst

[0256] 100 ml of toluene and 3.9 g of the support prepared in example33(C) were introduced into a 350 ml jacketed reactor equipped with ablade stirrer, thermometer, reflux condenser and a thermoregulatorsystem. The suspension was thermostatted at −10° C. and 50 ml of a 0.51M solution of MAO (178 mg Al/g support) was added over 20 minutes. Thiswas kept at −10° C. for 1 hour whilst stirring, heated to 0° C. for 1hour, 30° C. for 1 hour and finally 80° C. for 4 hours. The suspensionwas filtered, washed with 100 ml of toluene and once again 100 ml ofanhydrous toluene was added. After cooling to 0° C., a solutionconsisting of 50 ml of toluene and 194 mg of EBIZrCl₂ was added over 1hour. The reddish coloured solution was left at 0° C. for 1 hour andthen subsequently heated to 30° C. and kept stirred for 2 hours. Afterdecanting the solid, the liquid was filtered and the residue subjectedto two washings with 100 ml of toluene and one with 100 ml of anhydroushexane and finally dried under vacuo at 25° C. 6.5 g of spheroidalparticles was recovered, having the following composition: Zr=0.55%,Cl=1.1%, Al=10.2%.

EXAMPLE 35 Ethylene/1-butene copolymerization

[0257] It was worked according to the procedure described in example 11but using 1085 mg of the supported catalyst prepared in example 34.

[0258] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 36

[0259] (Comparison)

[0260] Preparation of a Supported Catalyst

[0261] 100 ml of anhydrous toluene and 5.15 g of the polystyrenic resinprepared in example 1 were introduced into a 350 ml glass reactor,provided with thermometer, reflux condenser, blade stirrer andthermoregulation system. The mixture, thermostatted at 0° C. and keptunder stirring, was added with 40 ml of a 0.74 M toluene solution ofmethylalumoxane (MAO). This was reacted at a temperature of 0° C. for 1hour, then at a temperature of 30° C. for 1 hour, then at a temperatureof 80° C. for 4 hours. After having cooled to 25° C., 50 ml of a toluenesolution containing 196.7 mg of ethylene-bis(indenyl)zirconiumdichloride were added within 30 minutes. The temperature was raised to30° C. whilst keeping stirred for 2 hours. A reddish solution wasobtained; this was allowed to decant, thus obtaining a precipitate and ayellowish solution which was removed by drainage. The precipitate wasrepeatedly washed with anhydrous toluene and thereafter dried undervacuum. 6 g of product showing microspheroidal morphology were obtained,having the following composition: Zr=0.26%, Cl=0.2%, Al=6.2%.

EXAMPLE 37

[0262] (Comparison)

[0263] Ethylene/1-butene copolymerization

[0264] It was worked according to the procedure described in example 8,but using 478 mg of the supported catalyst prepared in example 36(comparison).

[0265] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2.

EXAMPLE 38

[0266] (Comparison)

[0267] Preparation of a Functionalized Polystyrenic Support

[0268] 285 ml of methylene chloride and 16 g of a polystyrenic resin(Fluka product 4% DVB) were introduced into a 750 ml reactor equippedwith a mechanical stirrer and a thermostatting system. This was cooledto 10° C. and 41 g of aluminium trichloride in finely divided powderform were rapidly added. Maintaining the internal reactor temperature at10° C., 15.5 ml of acetyl chloride were added dropwise over 20 minutes.the reaction mixture was kept stirred at 25° C. for a further 24 hoursand then cautiously poured into a suspension consisting of 150 ml ofhydrochloric acid (37%) and 200 g of crushed ice. Once the addition wascompleted it was left whilst stirring for a further 30 minutes and,after filtration, the solid was repeatedly washed with distilled water,methanol, and acetone. The obtained product was then dried at 60° C.under vacuo. The solid product previously obtained was introduced,together with 75 ml-of methanol, into a 750 ml reactor equipped with amechanical stirrer and a thermostatting system. After thermostatting at30° C., a solution consisting of 9.2 g of NaBE₄, 11.5 ml of NaOH (20%)and 70 ml of distilled water was added. This was left to react at 35° C.for 72 hours, then slowly 100 ml of acetone was added to destroy theexcess NaBH₄. The resin was then filtered and repeatedly washed withdistilled water, acetone, methanol and acetone. This was then dried for4 hours at 400° C. 19 g of spherical product was obtained, having thefollowing characteristics: Functional groups  0.2 meq/g Surface area(B.E.T.) non detectable (Hg) 0.14 m²/g Porosity (B.E.T.) non detectable(Hg) 0.01 ml/g Average particle size  110 μm IR analysis peak at 1701cm⁻¹ (—C═O) broad peak at 3400 cm⁻¹ (—OH)

EXAMPLE 39

[0269] (Comparison)

[0270] Preparation of a Supported Catalyst

[0271] Into a 350 ml jacketed reactor equipped with a blade magneticstirrer, thermometer, reflux condenser and a thermoregulator system, 100ml of toluene and 5.6 g of the polystyrenic support prepared in example38 (comparison) were introduced. The suspension was thermostatted at−10° C. and 50 ml of 0.68 solution of MAO (166 mg Al/g support) wereadded over 60 minutes. This was kept at −100° C. for 1 hour, heated to0° C. for 1 hour, 30° C. for 1 hour and finally 80° C. for 3 hours. Thesuspension obtained was left to decant, the liquid separated and thesolid subjected to two washings with 100 ml of toluene and once againdispersed in 100 ml of anhydrous toluene. After cooling to 0° C., asolution consisting of 50 ml of toluene and 221 mg of EBIZrCl₂ was addedover 1 hour. The reddish coloured solution was left at 0° C. for 1 hourand then subsequently heated to 30° C. and kept stirred for 2 hours.After decanting the solid, the liquid was filtered and the residuesubjected to two washings with 100 ml of toluene and one with 100 ml ofanhydrous hexane and finally dried under vacuo at 25° C. 5.0 g ofspheroidal particles was recovered, having the following composition:Zr=0.09%, Cl=0.08%, Al=1.69%.

EXAMPLE 40

[0272] (Comparison)

Ethylene/1-butene copolymerization

[0273] It was worked according to the procedure described in example 11,but using 1460 mg of the supported catalyst prepared in example 39(comparison).

[0274] The polymerization conditions are reported in Table 1. The datarelating to the characterization of the obtained polymer are reported inTable 2. TABLE 1 ethylene hydrogen partial partial catalyst TIBALα-olefin pressure pressure time temperature Yield Activity Example (mg)(mmol) type (ml) (bar) (bar) (min) (° C.) (g) (g/gcat)  3  160 51-butene 181 165 0.05 120 50 174 1088  4  323 5 1-butene 4.95* 25.6 0.01120 50 130 402  5 2019# — 1-butene 2.55* 25.6 0.01 60 50 72 204  7  23510 — — 8.12 0.04 60 50 111 472  8  157 10 1-butene 517 16.5 0.05 120 50232 1474 11  108 10 1-butene 163 15.9 — 240 50 250 2300 12  390 10 — —9.6 — 120 80 110 281 16  121 10 1-butene 163 15.9 — 240 50 157 1293 18 165 10 1-butene 163 15.9 — 240 50 155 939 20  150 10 1-hexene 277 14.40.19 120 60 386 2563 26  538 10 1-butene 163 15.9 — 240 50 274 509 29 185 10 1-butene 163 15.9 — 240 50 204 1102 32  370 10 1-butene 181 16.50.05 120 50 102 273 35 1085 15 1-butene 163 15.9 — 240 50 96 88 37  47810 1-butene 581 16.5 0.05 60 50 389 814 (comp.) 40 1460 10 1-butene 16315.9 — 240 50 15 10 (comp.)

[0275] TABLE 2 absolute α-olefin I.V. density DSC Tamped BD Poured BDExample (wt. %) (dl/g) (g/ml) Tm (° C.) ΔH (J/g) (g/ml) (g/ml) Remarks 3 17 0.86 0.8985 88 68 0.45 0.41 granules  4 16 1.11 0.9100 72 69 0.380.35 ″  5 6.3 1.35 0.9310 110 115 0.41 0.38 ″  7 — 3.25 n.d. 134 1660.44 0.39 ″  8 13 1.92 0.9062 98 71 0.45 0.41 ″ 11 14.6 1.38 0.9030 8770 0.43 0.39 spheres 12 — 2.26 — 133 186 0.33 0.28 ″ 16 14.8 1.37 0.905690 83 0.45 0.39 ″ 18 14.5 0.86 0.9060 88 82 0.33 0.28 ″ 20 12.7* 2.370.9060 101 84 0.46 0.41 granules 26 11.9 1.65 0.9112 94 88 0.30 0.28spheres 29 14.1 1.51 0.9043 91 75 0.36 0.33 granules 32 16 0.89 0.911086 85 0.53 0.48 sferes 35 13.2 1.12 0.9085 95 63 0.45 0.38 ″ 37 (comp.)17.2 0.91 0.9024 92 62 0.24# 0.21# 15% powder, 85% agglomerate on thewall reactor 40 (comp.) n.m. 2.11 n.m. 96 47 n.d n.d agglomerate

[0276] TABLE 3 ethylene partial DSC catalyst TIBAL pressure timetemperature Yield Activity propylene Tm ΔH Example (mg) (mmol) (bar)(min) (° C.) (g) (g/gcat) (wt. %) (° C.) (J/g) Remarks 24 221.4 10 12.660 50 806 3640 60 — 0 divided spheres 25 20.0 10 10.5 120 50 164 8200 44— 0 ″

[0277] each other, are R¹ or two or four substituents R³ may form one ortwo rings having from 3 to 6 carbon atoms; substituents Q, same ordifferent form each other, are halogen, hydrogen, R¹, OR¹, SR¹, NR¹ ₂ orPR¹ ₂; m can be 0. or 1; n can be 0 or 1, being 1 if m=1; p can be 2 or3, preferably it is 3.

[0278] In the case of m=0, particulary suitable cyclopentadienylcompounds are those wherein the groups C₅R¹ _(5−m) are selected amongcyclopentadienyl, pentamethyl-cyclopentadienyl, indenyl and4,5,6,7-tetrahydroindenyl groups, and substituents Q are selected amongchlorine atoms and C₁-C₇ hydrocarbon groups, preferably methyl groups.

[0279] Non limitative examples of cyclopentadienyl compounds of formula(I), wherein m=0, are: (Cp)₂MCl₂ (MeCp)₂MCl₂ (BuCp)₂MCl₂ (Me₃Cp)₂MCl₂(Me₄Cp)₂MCl₂ (Me₅Cp)₂MCl₂ (Me₅Cp)₂MMe₂ (Me₅Cp)₂M(OMe)₂ (Me₅Cp)₂M(OH)Cl(Me₅Cp)₂M(OH)₂ (Me₅Cp)₂M(C₆H₅)₂ (Me₅Cp)₂M(CH₃)Cl (EtMe₄Cp)₂MCl₂[(C₆H₅)Me₄Cp]₂MCl₂ (Et₅Cp)₂MCl₂ (Me₅Cp)₂M(C₆H₅)Cl (Ind)₂MCl₂ (Ind)₂MMe₂(H₄Ind)₂MCl₂ (H₄Ind)₂MMe₂ {[Si(CH₃)₃]Cp}₂MCl₂ {[Si(CH₃)₃]₂Cp}₂MCl₂(Me₄Cp)(Me₅Cp)MCl₂ (Me₅Cp) MCl₃ (Me₅Cp)MBenz₃ (Ind)MBenz₃ (H₄Ind)MBenz₃(Cp)MBu₃ (Me₅Cp)MCl (Me₅Cp)MH

[0280] wherein Me=methyl, Et=ethyl, Bu=butyl, Cp=cyclopentadienyl,Ind=indenyl, H₄Ind=4,5,6,7-tetrahydroindenyl, Benz=benzyl, M 1 hour thenheated to 0° C. and kept at this temperature for 1 hour, at 30° C. for 1hour and finally heated to 80° C. for 4 hours. The whitish suspensionobtained was left to decant, the liquid separated and the solid wassubjected to two washings with 200 ml of toluene and one with 200 ml ofanhydrous hexane. After drying 66 g of spheroidal particles wererecovered: having the following composition: Al=7.5%, solvent=27%.

[0281] Using the same apparatus, 10.6 g of the resin treated with MAOwere dispersed in 300 ml of anhydrous toluene and cooled to 0° C. Asolution consisting of 50 ml of toluene and 176.8 mg of EBTHIZrCl₂ (7.7mg Zr/g support) were added over 1 hour. The solution was left at DOCfor 30 minutes and subsequently heated to 30° C. and kept stirred for 2hours. After decanting the solid, the liquid was filtered and theresidue subjected to two washings with 100 ml of toluene and one with100 ml of anhydrous hexane and finally dried under vacuo at 25° C. 8.7 gof spheroidal particles was recovered, having the following composition:Zr=0.40%, Cl=0.92%, Al=7.8%.

EXAMPLE 22 Ethylene/propylene copolymerization

[0282] Into a 4.25 litre steel autoclave, provided with agitator,manometer, temperature indicator, supplying system for the catalyst,feeding lines of the monomers and thermostatting

What is claimed is:
 1. A supported catalyst for the polymerization of olefins, comprising: (A) a porous organic support functionalised with groups having active hydrogen atoms; (B) at least one organo-metallic compound of aluminium containing at least one heteroatom selected from oxygen, nitrogen and sulphur; and (C) at least one compound of a transition metal selected from those of groups IVb, Vb or VIb of the Periodic Table of the Elements, containing at least one ligand of the cyclopentadienyl type.
 2. The supported catalyst according to claim 1, wherein the organic support has a porosity higher than 0.2 cc/g and a surface area higher than 30 m²/g.
 3. The supported catalyst according to claim 1, wherein the organic support is in the form of particles having micro-spheroidal morphology with a diameter comprised between 5 and 1000 μm.
 4. The supported catalyst according to claim 1, wherein the functional groups of the organic support are selected from hydroxy, primary amino, secondary amino, sulphonic, carboxylic, amido, N-monosubstituted amido, sulphonamido, N-monosubstituted sulphonamido, sulphydryl, imido and hydrazido groups.
 5. The supported catalyst according to claim 1, containing an amount of functional groups higher than 0.2 milli-equivalent for each gram of solid support.
 6. The supported catalyst according to claim 1, wherein the organic support is a partially cross-linked styrenic polymer.
 7. The supported catalyst according to claim 1, wherein the transition metal compound is selected from cyclopentadienyl compounds of formula (I): (C₅R¹ _(5−m))R_(m)(C₅R¹ _(5−m))_(m)MQ_(p−m)  (I) wherein M is Ti, Zr, Hf or V; C₅R¹ _(5−m) and C₅R¹ _(5−m) are cyclopentadienyl rings equally or differently substituted; substituents R¹, same or different from each other, are hydrogen, alkyl, alkenyl, aryl, alkaryl or aralkyl radicals containing from 1 to 20 carbon atoms which can also contain Si or Ge atoms or Si(CH₃)₃ groups, or also two or four substituents R¹ of a same cyclopentadienyl group can form one or two rings having from 4 to 6 carbon atoms; R² is a group which bridge links the two cyclopentadienyl rings and is selected from C³ ₂, C₂R³ ₄, SiR³ ₃, Si₂R³ ₄, GeR³ ₂, Ge₂R³ ₄, R³ ₂SiCR³ ₂, NR¹ or PR¹, with substituents R³, same or different from each other, which are R¹ or two or four substituents R³ can give one or two rings having from 3 to 6 carbon atoms; substituents Q, same or different from each other, are halogen, hydrogen, OH, SH, R¹, OR¹, SR¹, NR¹ ₂ or PR¹ ₂; m is 0 or 1; n is 0 or 1; being 1 when m=1; p is 2 or
 3. 8. The supported catalyst according to claim 1, wherein the organo-metallic compound of aluminium is an alumoxane.
 9. The supported catalyst according to claim 1, wherein the molar ratio between the organo-metallic compound of aluminium and the transition metal compound is comprised between 10 and
 500. 10. A process for the preparation of a supported catalyst for the polymerization of olefins according to any of claims 1 to 9, comprising the steps of: contacting in an inert solvent (A) a porous organic support functionalised with groups having active hydrogen atoms, and (B) at least one organo-metallic compound of aluminium containing at least one heteroatom selected from oxygen, nitrogen and sulphur; thereafter contacting the thus obtained product with (C) at least one compound of a transition metal selected from those of groups IVb, Vb or VIb of the Periodic Table of the Elements, containing at least one ligand of the cyclopentadienyl type; and finally recovering the supported catalyst by removing the solvent.
 11. A process for the preparation of a supported catalyst for the polymerization of olefins according to any of claims 1 to 9, comprising the steps of: contacting in an inert solvent (B) at least one organo-metallic compound of aluminium containing at least one heteroatom selected from oxygen, nitrogen and sulphur, and (C) at least one compound of a transition metal selected from those of groups IVb, Vb or VIb of the Periodic Table of the Elements, containing at least one ligand of the cyclopentadienyl type; thereafter contacting the thus obtained product with (A) a porous organic support functionalised with groups having active hydrogen atoms; and finally recovering the supported catalyst by removing the solvent.
 12. A process for the preparation of a supported catalyst for the polymerization of olefins according to any of claims 1 to 9, comprising the steps of: contacting in an inert solvent (A) a porous organic support functionalised with groups having active hydrogen atoms, and (B) at least one organo-metallic compound of aluminium containing at least one heteroatom selected from oxygen, nitrogen and sulphur; contacting in an inert solvent (B) at least one organo-metallic compound of aluminium containing at least one heteroatom selected from oxygen, nitrogen and sulphur, and (C) at least one compound of a transition metal selected from those of groups IVb, Vb or VIb of the Periodic Table of the Elements, containing at least one ligand of the cyclopentadienyl type; thereafter contacting the product obtained by contacting (A) and (B) with the product obtained by contacting (B) and (C); and finally recovering the supported catalyst by removing the solvent.
 13. The process according to any of claims 10 to 12, wherein the organic support is pre-contacted with at least an aluminium alkyl compounds of formula (VI): R⁵ _(q)AlX_(3−q)  (VI) wherein R⁵ is selected among alkyl, alkenyl, aryl, alkaryl and aralkyl radicals containing from 1 to 10 carbon atoms, X is selected among hydrogen and halogen atoms, q is an integer comprised between 1 and
 3. 14. The process according to claim 13, wherein the aluminuim alkyl compound is triisobutylaluminium.
 15. A supported and pre-polymerized catalyst for the polymerization of olefins obtainable by subjecting a supported catalyst according to any of claims 1 to 9 to a pre-polymerization treatment with at least one olefinic monomer.
 16. A supported and pre-polymerized catalyst according to claim 15, wherein the amount of polymer produced is comprised between 0.5 and 10 parts by weight with respect to the weight of the supported catalyst.
 17. The supported and pre-polymerized catalyst according to any of claim 15 or 16, comprising an alkyl aluminium compound of formula (VI): R⁵ _(q)AlX_(3−q)  (VI) wherein R⁵, X and q are defined as above.
 18. A process for the homo- or co-polymerization of olefins comprising the polymerization reaction of one or more olefinic monomers in the presence of a supported catalyst according to any of claims 1 to
 9. 19. A process for the homo- or co-polymerization of olefins comprising the polymerization reaction of one or more olefinic monomers in the presence of a supported and prepolymerized catalyst according to any of claims 15 to
 17. 20. The process for the homo- or co-polymerization of olefins according to any of claim 18 or 19, wherein the catalyst is pre-contacted with at least one compound selected from the alkyl aluminium compounds of formula (VI): R⁵ _(q)AlX_(3−q)  (VI) wherein R¹, X and q are defined as above, and the organo-metallic compounds of aluminium containing at least one heteroatom selected from oxygen, nitrogen, sulphur.
 21. The process for the homo- or co-polymerization of olefins according to claim 20, wherein the organo-metallic compounds of aluminium are alumoxanes. 